Unprecedented Ultraviolet Circularly Polarized Light‐Dependent Anomalous Photovoltaics in Chiral Hybrid Perovskites

Abstract Circularly Polarized Light (CPL)‐dependent anomalous photovoltaic effect (APVE), characterized by light helicity‐manipulated steady photocurrent and above‐bandgap photovoltage, has demonstrated significant potential in the fields of photoelectronic and photovoltaics. However, exploiting CPL‐dependent APVE in chiral hybrid perovskites, a promising family with intrinsic chiroptical activity and non‐centrosymmetric structure, remains challenging. Here, leveraging the flexible structural design of chiral alternating cations intercalation‐type perovskites, CPL‐dependent APV, for the first time, is achieved in chiral perovskites. Specifically, by introducing lone pair electrons into the organic layers to greatly amplify the polarization, [(R)‐PPA](MOPA)PbBr₄ (2‐R) (PPA = 1‐phenylpropylammonium, MOPA = 3‐methoxypropylammonium) exhibit intrinsic APVE with an above‐bandgap photovoltage of 6.50 V (E_g = 3.01 eV) under ultraviolet (UV) light illumination. Strikingly, profiting from the natural chiral optical activity of chiral perovskites, unprecedented UV CPL‐dependent APV is realized in 2‐R, driving the high distinguishability between right‐hand and left‐hand CPLs with a large anisotropy factor (g_Iph) of 0.33. This study pioneers the realization of CPL‐dependent APV within chiral perovskite, promising significant advancements in optoelectronic device technologies.